Demulsifier and dispersant for treating petroleum crude oils and biofuels prior to desalter and heater treater processing

ABSTRACT

A demulsifier and dispersant for treating petroleum crude oils and biofuels prior to desalter and heater treater processing can also be used to treat slop oils and clean drill cuttings.

CROSS-REFERENCE TO RELATED APPLICATIONS

This is anon-provisional patent application of U.S. Provisional Patent Application Ser. No. 61/684,414, filed 17 Aug. 2012, which is hereby incorporated herein by reference.

Priority of U.S. Provisional Patent Application Ser. No. 61/684,414, filed 17 Aug. 2012, incorporated herein by reference, is hereby claimed.

All prior patents and patent applications naming me as an inventor are hereby incorporated herein by reference, including the following:

Published U.S. patent applications: US20110174695 A1; US2006/0035793 A1; U. S. 2005/0193923 A1; US2009/059046; US2005/26355; PCT International Publication Number WO2006/012622 A2; U.S. patent application Ser. No. 13/302,645; U.S. patent application Ser. No. 13/121,729; U.S. Pat. No. 6,322,621 B1; U.S. Pat. No. 6,783,582 B2; U.S. Pat. No. 7,449,429; and U.S. Pat. No. 8,063,004.

STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT

Not applicable

REFERENCE TO A “MICROFICHE APPENDIX”

Not applicable

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to processing of fuel, and more particularly to dewatering agents for fuels and cleaning agents for drill cuttings and dewatering and dispersing agents for biofuels.

2. General Background of the Invention

Processing of fuel often involves adding to the fuel dewatering agents for fuels and dewatering and dispersing agents for biofuels. Cleaning agents are often used to clean drill cuttings.

BRIEF SUMMARY OF THE INVENTION

The present invention includes a composition which can be useful for cleaning drill cuttings, processing slop oil, and processing biofuels. The composition preferably includes a demulsifier, a co-additive for demulsifier, a solvent and coupling agent and antifoaming agent, a very powerful demulsifier, a solvent, a chelating dispersant, a surfactant, a fluorinated surfactant, and a dispersant which is an oil soluble and water dispersible anionic surfactant. Preferably there are as well multiple surfactant -degreasing agents (particularly when the composition is used to clean drill cuttings).

Preferably, the demulsifier is at least one from the group consisting of citric acid, acetic acid, ascorbic, formic, other carboxylic acids, sulphamic acid, phosphoric acid, sulfuric acid, and mixtures thereof, the co-additive for demulsifier is at least one from the group consisting of dodecyl benzene sulphonic acid, toluene sulphonic acid, toluene sulphonic acid, xylene sulphonic acid, and any other alkyl benzene sulphonic acid, and mixtures thereof, the solvent and coupling agent and antifoaming agent—hydrotrope is at least one from the group consisting of butyl cellosolve and any other preferably non-toxic alkyl glycol ether, and mixtures thereof,

-   the very powerful demulsifier is at least one from the group     consisting of on the one hand diisopropylnaphthalenesulphonic acid     (35-70%), sodium dodecylbenzenesulfonate (10-30%),     1,2,4-trimethylbenzene (5-15%), sulphuric acid (0.5-5%), xylene     (0-3%), cumene (0-3%) and on the other hand other alkyl, di-alkyl,     tri-alkyl napthlalene sulphonic acids, and mixtures thereof, the     solvent is at least one from the group consisting of pine oil and     any other terpene type of oil, and mixtures thereof, the chelating     dispersant chelates Fe, Al, Ca from about 100 ppm to less than 10     ppm—moves Fe, Al, Ca from oil to water, and comprises an oil-water     soluble copolymer of partially sulfonated, maleic anhydride and     polystyrene, 25% active, the surfactant lowers surface tension and     is at least one from the group consisting of alcohol ethoxylate and     any other non-ionic ethoxylated surfactant, and mixtures thereof,     the fluorinated surfactant lowers surface tension is at least one     from the group consisting of on the one hand 40% fluorosurfactant,     30% isopropyl alcohol, and 30% water and on the other hand a     Capstone fluorinated surfactant, such as Capstone N35 or Capstone     N65fluorinated surfactant, which are 25% active, so 4× the amount     should be used, and mixtures thereof, the surfactant—degreasing     agents are at least one from the group consisting of nonylphenol     ethoxylate, POE-4, nonylphenol ethoxylate, POE-6, and nonylphenol     ethoxylate, POE-8, and mixtures thereof, the dispersant is an oil     soluble and water dispersible anionic surfactant which drops char     content from around 2000 ppm to less than 10 ppm and is at least one     from the group consisting of isopropylamine dodecyl benzene     sulfonates and other oil soluble and water dispersible anionic     surfactants, including other isopropylamine dodecyl benzene     sulfonates, and mixtures thereof.

DETAILED DESCRIPTION OF THE INVENTION

TABLE 1 A preferred formula for the composition (to be sold as Malcera 1507AK) of the present invention Col. 5 Col. 6 Col. 2 Col. 4 More Most Col. 7 Col. 8 Col. 1 Function Col. 3 Preferred Preferred Preferred Example A Example B Row Ingredient (Generic name) ((alternatives)) % by wt. % by wt. % by wt. % by wt. % by wt. % by wt. 1 Citric Acid demulsifier 30 to 90 40 to 80 45 to 75 50 to 70 59.04 60.5 50% (citric acid 50%/water 50%) ((acetic acid, sorbic acid, formic acid, butyric acid, gluconic acid, valeric acid, 2-ethylbutyric acid, 2-ethylhexoic acid, propionic acid, iso pentanoic acid, benzoic acid, and other carboxylic acids; mineral acids, including nitric acid, phosphoric acid, and sulfuric acid; sulfonic acids, including DDBSA-Biosoft 101 and toluene sulfonic acid; fatty acids derived from vegetable oils, including mysistic, palmitic, stearic acid, oleic acid, linoleic acid, lauric acid, and linolenic acid; and mixtures thereof)) 2 Biosoft co-additive for demulsifier (dodecyl 3 to 30 5 to 25 5 to 20 5 to 15 5.4 15 101- benzene sulphonic acid) ((toluene sulphonic DDBSA acid or any other alkyl benzene sulphonic acid, such as toluene sulphonic acid, xylene sulphonic acid and mixtures thereof)) 3 butyl solvent and coupling agent and antifoaming 2 to 8 3 to 8 3.0 to 7.0 3.0 to 5.0 2.4 3.0 cellosolve agent - hydrotrope (butyl cellosolve, aka EB) ((any other alkyl glycol ether, preferably non-toxic)) 4 C-4100 very powerful demulsifier 3 to 25 5 to 20 7 to 15 9 to 12 10.0 9 (diisopropylnaphthalenesulphonic acid (35- 70%), sodium dodecylbenzenesulfonate (10-30%), 1,2,4-trimethylbenzene (5-15%), sulphuric acid (0.5-5%), xylene (0-3%), cumene (0-3%)) ((other alkyl, di-alkyl, tri-alkyl napthlalene sulphonic acids)) 5 Pine Oil solvent (pine oil) ((any other terpene type of 0.5 to 5 0.5 to 3.0 0.8 to 3.0 1.0 to 3.0 1.2 1.5 oil)) 6 Versa-TL- chelating dispersant - chelates Fe, Al, Ca 1 to 12 2 to 10 2 to 8 2 to 6 5.7 6 4 from about 100 ppm to less than 10 ppm - moves Fe, Al, Ca from oil to water (an oil-water soluble copolymer of partially sulfonated, maleic anhydride and polystyrene, 25% active) ((Versa-TL-3 diluted with water to 25% active)) 7 Merpol SE surfactant - lowers surface tension (alcohol 0.5 to 3.0 0.5 to 2.5 0.5 to 2.0 0.5 to 1.5 1.1 1.0 ethoxylate) ((any other non-ionic ethoxylated surfactant)) 8 Zonyl FSN fluorinated surfactant - lowers surface 0.01 to 0.3 0.01 to 0.2 0.05 to 0.18 0.05 to 0.15 0.11 0.10 tension (40% fluorosurfactant, 30% isopropyl alcohol, and 30% water) ((or a Capstone fluorinated surfactant, such as Capstone N35 or Capstone N65 fluorinated surfactant, which are 25% active, so 4X the amount should be used)) 9 Makon 4 surfactant - degreasing agent (nonylphenol 0.25 to 2.0 0.25 to 1.0 0.25 to 0.70 0.3 to 0.7 0.35 0.5 ethoxylate, POE-4) ((or other nonylphenol ethoxylates, such as Makon 6 or Makon 8)) 10 Makon 6 surfactant - degreasing agent (nonylphenol 0.25 to 2.0 0.25 to 1.0 0.25 to 0.70 0.3 to 0.7 0.35 0.5 ethoxylate, POE-6) ((or other nonylphenol ethoxylates, such as Makon 4 or Makon 8)) 11 Makon 8 surfactant - degreasing agent (nonylphenol 0.25 to 2.0 0.25 to 1.0 0.25 to 0.70 0.3 to 0.7 0.35 0.5 ethoxylate, POE-8) ((or other nonylphenol ethoxylates, such as Makon 4 or Makon 6)) 12 Biosoft N- dispersant - oil soluble and water 2.0 to 20 2.0 to 17 2.0 to 15 2.0 to 13.0 14.0 2.4 411 dispersible anionic surfactant - drops char content from around 2000 ppm to less than 10 ppm (isopropylamine dodecyl benzene sulfonates) ((other oil soluble and water dispersible anionic surfactants, including other isopropylamine dodecyl benzene sulfonates)) In the above table, POE is polyoxiethylene.

To make the product, one blends as follows (with preferably constant stirring): put the citric acid in a reactor at ambient temperature (typically around 25 Centigrade);

-   then add Biosoft101, -   then add EB, -   then add C-4100, -   then add Pine Oil, -   then slowly add Versa TL-4 until no foam is present, -   then add Merpol SE, -   then add Zonyl FSN, -   then add Makon 4, -   then add Makon 6, -   then add Makon 8, -   then add Biosoft N-411. -   Then continue to stir for 4 hours at ambient temperature.

Preferably, the citric acid is always the first ingredient in the reactor. Preferably, EB, Biosoft 101, and C-4100 are added before Versa TL-4. After that, the ingredients can be added in any order. The goal is to keep all components properly blended without separation as the blending occurs.

However, it is possible to mix ingredients other than citric acid together, then add that mix while stirring to the citric acid (in such a case more EB might be needed).

Malcera sells the above product as Malcera 1507AK.

Malcera 1507AK (optionally without Makon 4, Makon 6, and Makon 8) (or a version with ingredients from columns 1 and or 2) can be used to treat slop oils and tank remnants or sludges to knock out water and to disperse the hydrocarbons into diluents, and to drop solids out of these products. This is usually performed at about 150-200 degrees F. and the concentration is usually 1,000-2,500 ppm.

Malcera 1507AK (or a version with ingredients from columns 1 and or 2) can be used to treat drill cuttings to reduce water content. This is usually performed at about 100 degrees C. and the concentration is usually 5,000-10,000 ppm. The drill cuttings are typically coated with oil based drilling mud emulstions.

Malcera 1507AK (optionally without Makon 4, Makon 6, and Makon 8, but preferably in approximately the amounts listed in column 7 of Table 1) (or a version with ingredients from columns 1 and or 2) can be used to reduce water content and solids content in a biofuels mixture made from the pyrolysis of wood to yield a very clean oil. This clean oil can then be hydrotreated to make gasoline and diesel. When used in a biofuels mixture, typically 500-1000 ppm of Malcera 1507AK is used in the biofuels mixture. The typical temperature is about 150 degrees F. Malcera 1507AK knocks out water so that less than 99.9% of the biofuels mixture is water. A desalter then takes out last up to 0.1% water.

All measurements disclosed herein are at standard temperature and pressure, at sea level on Earth, unless indicated otherwise.

The foregoing embodiments are presented by way of example only; the scope of the present invention is to be limited only by the following claims. 

1. A composition including the ingredients listed in Rows 1-12 of Column 1 and/or Column 2 of Table 1 in the specification, wherein at least one ingredient is included from each row.
 2. The composition of claim 1, wherein the ingredients are those listed in Column
 1. 3. The composition of claims 1, wherein the ingredients are in the ranges listed in Column
 3. 4. The composition of claims 1, wherein the ingredients are in the ranges listed in Column
 4. 5. The composition of claims 1, wherein the ingredients are in the ranges listed in Column
 5. 6. The composition of claims 1, wherein the ingredients are in the ranges listed in Column
 6. 7-8. (canceled)
 9. A method of treating slop oil and tank remnants or sludges to knock out water and to disperse the hydrocarbons into a diluent, and to drop solids out of these products, comprising: heating the slop oil and tank remnants or sludges to about 130-200 degrees F. (54-93.3 degrees C.) in a vessel; adding a diluent comprising at least one from the group consisting of crude oil, petroleum hydrocarbons derived from crude oil, and biofuels to the vessel in an amount of at least 50 parts diluent to 100 parts slop oil and tank remnants or sludges; adding the composition of any one of claims 1-8 to the vessel in a concentration of about 500-3,000 ppm; maintaining the heat at about 130-200 degrees F. (54-93.3 degrees C.) for about 30 minutes to 3 hours with stirring until there is not more than 5% water in the solution and the slop oil and tank remnants or sludges disperse into the diluent.
 10. The method of claim 9, wherein the diluent comprises at least one from the group consisting of crude oil, refined petroleum hydrocarbons derived from crude oil, and biofuels including biodiesel
 11. A method of treating drill cuttings to reduce water content, comprising: heating the drill cuttings to about 90-120 degrees C. in a vessel; adding the composition of any one of claims 1-8 to the vessel in a concentration of about 1,000-10,000 ppm; maintaining the heat at about 90-120 degrees C. for about 30 minutes to 3 hours with mixing until the drill cuttings are at least 98% oil free and oil recovered from the cuttings is at least 99% water free.
 12. A method of reducing water content and solids content in a biofuels mixture made from the pyrolysis of wood, the method comprising: heating the biofuels mixture to about 130-150 degrees F. (54-65.6 degrees C.); adding to the biofuels mixture about 500-3000 ppm of the composition of any one of claims 1-8; maintaining the heat at about 130-150 degrees F. (54-65.6 degrees C.) until at least 99% of the mixture is water-free.
 13. The method of claim 11, wherein a desalter then takes out water remaining in the mixture.
 14. A composition including the ingredients listed in Rows 1-8 and 12 of Column 1 and/or Column 2 of Table 1 in the specification, wherein at least one ingredient is included from each row.
 15. The composition of claim 14, wherein the ingredients are those listed in
 16. The composition of claims 14, wherein the ingredients are in the ranges listed in Column
 3. 17. The composition of claims 14, wherein the ingredients are in the ranges listed in Column
 4. 18. The composition of claims 14, wherein the ingredients are in the ranges listed in Column
 5. 19. The composition of claims 14, wherein the ingredients are in the ranges listed in Column
 6. 20-21. (canceled)
 22. The composition of claim 14, further comprising at least one ingredient from rows 9-11.
 23. The composition of claim 14, further comprising at least two ingredients from rows 9-11.
 24. A method of treating slop oil and tank remnants or sludges to knock out water and to disperse the hydrocarbons into a diluent, and to drop solids out of these products, comprising: heating the slop oil and tank remnants or sludges to about 130-200 degrees F. (54-93.3 degrees C.) in a vessel; adding a diluent comprising at least one from the group consisting of crude oil, petroleum hydrocarbons derived from crude oil, and biofuels to the vessel in an amount of at least 50 parts diluent to 100 parts slop oil and tank remnants or sludges; adding the composition of any one of claims 14-23 to the vessel in a concentration of about 500-3,000 ppm; maintaining the heat at about 130-200 degrees F. (54-93.3 degrees C.) for about 30 minutes to 3 hours with stirring until there is not more than 5% water in the solution and the slop oil and tank remnants or sludges disperse into the diluent.
 25. The method of claim 24, wherein the diluent comprises at least one from the group consisting of crude oil, refined petroleum hydrocarbons derived from crude oil, and biofuels including biodiesel.
 26. A method of reducing water content and solids content in a biofuels mixture made from the pyrolysis of wood, the method comprising: heating the biofuels mixture to about 130-150 degrees F. (54-65.6 degrees C.); adding to the biofuels mixture about 500-3000 ppm of the composition of any one of claims 14-23; maintaining the heat at about 130-150 degrees F. (54-65.6 degrees C.) until at least 99% of the mixture is water-free.
 27. The method of claim 26, wherein a desalter then takes out water remaining in the mixture.
 28. (canceled) 